JP2008088305A - Perfluorofluororesin composite composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a perfluorofluororesin composite composition composed of a perfluorofluororesin composite composition in which an inorganic layered compound is uniformly dispersed in a perfluorofluororesin at a nano-level and having excellent dynamic properties and high zero shear rate viscosity, to provide a method for producing the composition and to provide a molded product composed of the composition. <P>SOLUTION: The perfluorofluororesin composite composition is a resin composite composition in which the inorganic layered compound having properties of swelling or cleaving in a dispersion medium is dispersed in the perfluorofluororesin and has the ratio (V<SB>0.1</SB>/V<SB>1</SB>) of viscosity (V<SB>0.1</SB>) at 0.1 rad/s measured at 340°C to viscosity (V<SB>1</SB>) at 1 rad/s measured at 340°C of ≥1.5 by a parallel plate mode of a dynamic viscoelasticity measuring apparatus. The method for producing the composition and the molded product composed of the composition are provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  In the present invention, the mechanical properties of the inorganic layered compound uniformly dispersed at the nano level in the fluororesin are improved, and the melt viscosity does not approach a constant value even if the shear rate or shear rate is reduced, and further zero shear is achieved. The present invention relates to a perfluorofluororesin composite composition having a high viscosity (Zero Shear Rate Viscosity) and a method for producing the same.

  Tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) ) Copolymers (EPE) etc. are processed by melt molding such as extrusion molding, blow molding, injection molding, etc., but the products such as tubes, hoses, containers, electric wires, etc. are heat and chemical resistant. It has excellent characteristics such as high-frequency electrical characteristics, non-adhesiveness, and flame retardancy, so it can be used as piping for transporting chemicals such as acids and alkalis, solvents, paints, joints and chemical storage containers, and pipes and tanks. It is widely used as a lining for electric wires, etc., or as a wire coating material. However, these fluororesins, particularly perfluorofluororesin copolymers, have a problem in mechanical properties because they have almost no intermolecular interaction. In addition, perfluoro fluoropolymer copolymer is a flame retardant material that is difficult to burn. However, it has been pointed out that hot fluororesin drops (drip) when a fire breaks out, generating smoke and spreading fire. ing.

  Recently, many techniques for improving the mechanical properties, heat distortion temperature, chemical resistance, gas permeability, etc. by directly melting and mixing nanoparticles such as inorganic fine particles with polymer materials have been made. However, when inorganic fine particles or inorganic nanoparticles are melt-mixed with resin, the agglomeration force of the fine particles increases as the particle size decreases, causing reaggregation of the particles. It is extremely difficult to nano-disperse as it is (The 47th Conference of the Japan Society for the Science of Materials, Vol. 47, P150, 2003).

  In order to solve such problems, many research examples have been reported in which organic layered inorganic layered compounds are nano-dispersed in polymer materials, but the polymer used is a polar resin such as a polyamide resin. There are many. In addition, there was an attempt to disperse the organically modified inorganic layered compound in the fluororesin, but the inorganic layered compound was nanodispersed in the partially fluorinated resin such as polyvinylidene fluoride (PVDF). / Perfluoro fluororesin such as HEP copolymer (FEP) has not been successfully nanodispersed (Journal of Applied Polymer Science, P1061, 2004). Japanese Patent Application Laid-Open No. 2000-204214 describes a fluororesin nanocomposite obtained by melting and mixing mainly a fluororubber and an organically treated inorganic layered compound. There is no description.

  As an example of nano-dispersing an inorganic layered compound in a perfluorofluororesin, for example, Japanese Patent Application Laid-Open No. 2001-523278 is obtained by melt-mixing an inorganic layered compound treated with an organized phosphonium and a perfluorofluororesin. Improvements in mechanical properties of perfluorofluororesin composites have been reported. However, there is no description about the evaluation results such as X-ray measurement or electron microscope observation necessary for confirming whether the inorganic layered compound is nano-dispersed in the perfluoro fluororesin, and the improved elastic modulus of the perfluoro fluororesin composite Is less than twice that of the perfluorofluororesin alone. Furthermore, since the inorganic layered compound is treated with organic phosphonium, there is a problem in chemical resistance and heat resistance of the obtained perfluorofluororesin composite.

  WO 2004/074371 A1 discloses that an inorganic layered compound treated with organic phosphonium and a functional group-containing heat-meltable fluororesin are put into a heat-meltable fluororesin and melt-mixed together to obtain a heat-meltable fluororesin. A fluororesin composite composition having improved mechanical properties such as gas resistance / chemical solution permeability and elastic modulus is described. However, since the functional group-containing heat-meltable fluororesin is contained in addition to the organic phosphonium, the heat resistance of the obtained fluororesin composite composition is further deteriorated and the expensive functional group-containing heat-meltable fluororesin Economic problems due to use also arise.

  Further, JP-A-2004-10891 discloses a fluororesin composite composition in which an inorganic layered compound not subjected to organic treatment is nanodispersed in a fluororesin such as polychlorotrifluoroethylene (PCTFE). Improvements in mechanical properties and storage elastic modulus at room temperature or at a high temperature of 100 ° C. or higher while maintaining chemical resistance and heat resistance are described. The fluororesin composite composition is prepared by mixing an aqueous fluororesin latex such as PCTFE and a dispersion of an inorganic layered compound that has not been organically treated to precipitate and separate the solid phase from the aqueous mixture and drying. can get. However, the storage elastic modulus at a high temperature (150 ° C.) of the fluororesin composite composition exhibiting a polarity like PCTFE has increased to about 2.5 times that of the fluororesin used alone, but it has almost no polarity and is completely It is not described whether such a storage elastic modulus improvement can be obtained even with a hydrophobic perfluorofluororesin composite. In addition, the thixotropy characteristics of the fluororesin composite composition melt are not described at all. Also, a method for precipitating and separating a solid phase from an aqueous mixture obtained by mixing a dispersion of an aqueous resin latex and an inorganic stratiform compound, drying, and nanodispersing the inorganic stratiform compound in a resin matrix is disclosed in JP-A-2004-10891. Have already been reported (for example, Chinese published patent CN12338353A or Journal of Applied Polymer Science, P1873 and P1879, 2000).

  On the other hand, perfluoro fluororesin is used as an insulation and jacket material for communication cables (plenum cables) because of its excellent electrical properties, flame retardancy and heat resistance. The perfluoro fluororesin for these communication cables has a lower melt viscosity (or higher melt flow rate (MFR)), and the wire extrusion property becomes better, but the communication cable made of perfluoro fluororesin has a low melt viscosity. In the case of fire, high temperature droplets drop (drip), causing smoke generation and fire spread, so the flame retardancy of the cable to prevent fire spread due to the cable is strictly defined ( For example, US NPFA-255 standard). Therefore, in wire extrusion molding with a high shear rate, the melt viscosity is low and the moldability is excellent.On the other hand, after extrusion to form an electric wire, the dripping is generated even if a fire occurs. There is a demand for a perfluoro fluororesin having a high so-called zero shear viscosity in which the melt viscosity becomes high and drip hardly occurs.

  As a perfluoro fluororesin composition for preventing drip, for example, US Published Patent Application No. 2005 / 0187328A1 discloses a large amount of inorganic filler such as 10% to 60% zinc oxide and a decrease in physical properties in perfluoro fluororesin. Improved drip properties are described by blending a small amount of hydrocarbon resin to prevent. However, the use of a large amount of an inorganic filler such as zinc oxide causes a problem that other physical properties of the perfluorofluororesin are impaired. Moreover, since zinc oxide and perfluoro fluororesin are directly melt-mixed, a conventional microcomposite with poor high-speed extrusion moldability can be obtained and cannot be made into a nanocomposite. On the other hand, in the nanocomposite, the extrusion speed does not decrease, and the thin wall extrusion becomes possible.

JP 2000-204214 A JP-T-2001-523278 JP 2004-10891 A WO2004 / 074371 A1 Publication Chinese published patent CN12338353A US Published Patent No. 2005 / 0187328A1 Journal of Applied Polymer Science, P1061, 2004 47th Annual Conference of the Japan Society for Materials Research, Vol.47, P150, 2003 Journal of Applied Polymer Science, P1873, P1879, 2000

The present inventor has disclosed a perfluoro fluororesin emulsion (hereinafter sometimes referred to as latex) and a dispersion medium in which the fluororesin primary particles are surrounded by a surfactant (hereinafter sometimes referred to as an emulsifier) and stably dispersed in a solvent. The aqueous dispersion obtained by uniformly mixing the resin primary particles and the swollen or cleaved inorganic layered compound at a temperature of 0 ° C. or lower is stirred with the dispersion containing the inorganic layered compound having the property of swelling or cleaving into After freezing, adding an electrolytic substance to change the ionic strength or pH of the mixed solution, or applying a shearing force to fix the uniform mixing state of the fluororesin primary particles and the inorganic layered compound (hereinafter this process) The resulting aggregate is separated from the aqueous solution and dried to allow the inorganic layered compound to be uniformly dispersed in the resin at the nano level. Fluororesin composite composition, while maintaining excellent heat resistance and mechanical properties, and found to exhibit a high zero shear viscosity in the molten state.
An object of the present invention is a perfluoro fluororesin composite having a high zero shear viscosity and excellent mechanical properties comprising a perfluoro fluororesin composite composition in which an inorganic layered compound is uniformly dispersed at a nano level in a fluororesin resin. It is to provide a composition and a method for producing the composition.

The present invention relates to a resin composite composition in which an inorganic layered compound having a property of swelling or cleaving in a dispersion medium is dispersed in a perfluorofluororesin, and in a parallel plate mode of a dynamic viscoelasticity measuring apparatus. Perfluoro fluorine having a ratio (V _0.1 / V ₁ ) of 1.5 or more at a viscosity (V ₁ ) at ₁ rad / sec and a viscosity (V _0.1 ) at _0.1 rad / sec measured at 340 ° C. A resin composite composition is provided.

  The perfluorofluororesin composite composition described above, wherein the perfluorofluororesin is a polymer or copolymer of a monomer selected from tetrafluoroethylene, hexafluoropropylene, and perfluoro (alkyl vinyl ether), This is a preferred embodiment of the invention.

  The perfluoro fluororesin described above, wherein the inorganic layered compound having a property of swelling or cleaving into the dispersion medium is an inorganic layered compound selected from the group consisting of a smectite group viscosity mineral, a swellable mica group viscosity mineral, and a combination thereof. The composite composition is a preferred embodiment of the present invention.

  The perfluorofluororesin composite composition described above, wherein the content of the inorganic layered compound in the perfluorofluororesin composite composition is 0.5 to 15% by weight with respect to the fluororesin composite, is a preferred embodiment of the present invention. It is.

  The above-mentioned perfluoro fluorine resin composite composition in which the thickness of the inorganic layered compound dispersed in the perfluoro fluorine resin composite composition is 100 nm or less is a preferred embodiment of the present invention.

  The present invention relates to an aggregate obtained by aggregating an aqueous dispersion mixture obtained by mixing a perfluoro fluororesin emulsion and a dispersion containing an inorganic layered compound having a property of swelling or cleaving into a dispersion medium with stirring. Provided is a method for producing the above-mentioned perfluorofluororesin composite composition by separating and drying an aqueous component.

  The aggregate is obtained by aggregating the aqueous dispersion mixture by freezing at a temperature of 0 ° C. or lower, adding an electrolytic substance to change the ionic strength or pH of the mixture, or applying a shearing force. The method for producing the perfluorofluororesin composite composition is a preferred embodiment of the present invention.

  A pellet obtained by melt-extruding the perfluorofluororesin composite composition obtained by drying the perfluorofluororesin composite composition is a preferred embodiment of the present invention.

  The present invention also provides an electric wire or an electric wire covering jacket comprising the above-mentioned perfluoro fluorine resin composite composition.

  The present invention also provides a tube or sheet comprising the perfluorofluororesin composite composition described above.

  The present invention also provides a blow molded article comprising the perfluorofluororesin composite composition described above.

According to the present invention, a perfluoro fluororesin composite composition having excellent mechanical properties and a high zero shear viscosity, comprising a perfluoro fluororesin composite composition in which an inorganic layered compound is uniformly dispersed at a nano level in a fluororesin resin. Is provided.
According to the present invention, there are provided various molded articles having excellent performance comprising a perfluoro fluororesin composite composition having a high zero shear viscosity.

  Examples of the perfluorofluororesin used in the present invention include polymers or copolymers of perfluoromonomers such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and perfluoroalkyl vinyl ether (PAVE). be able to. Specific examples of the perfluorofluororesin include polytetrafluoroethylene (hereinafter referred to as PTFE), TFE / PAVE copolymer (hereinafter referred to as PFA), TFE / HEP copolymer (hereinafter referred to as FEP), Examples thereof include a TFE / HEP / PAVE copolymer (hereinafter referred to as EPE). Among these, in the copolymer of tetrafluoroethylene and perfluoro (alkyl vinyl ether), the alkyl group of perfluoro (alkyl vinyl ether) preferably has 1 to 5 carbon atoms, particularly 1 to 3 carbon atoms. Further, these polymers or copolymers may be blended and used.

  The fluororesin emulsion used in the present invention is an emulsion containing the above-mentioned perfluorofluororesin. For example, as the perfluoro fluororesin emulsion, a perfluoro fluororesin emulsion such as a polymer or copolymer of a monomer selected from tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and perfluoroalkyl vinyl ether (PAVE). Can be mentioned. As the fluororesin emulsion, conventionally known ones can be appropriately selected and used. Emulsions of these polymers are usually produced by emulsion polymerization.

  In the present invention, the resin primary particles and the swollen or cleaved inorganic layered compound are uniformly stirred by stirring the perfluorofluororesin emulsion and the dispersion containing the inorganic layered compound having the property of swelling or cleaving into the dispersion medium. The mixed aqueous dispersion is agglomerated to fix the uniform mixed state of the fluororesin primary particles and the inorganic stratiform compound, and then the obtained agglomerate is separated from the aqueous solution and dried to obtain the inorganic stratiform compound. It is possible to obtain a perfluorofluororesin composite composition that is uniformly dispersed in the resin at a nano level.

  Therefore, in the present invention, after mixing a dispersion containing an inorganic layered compound in which a part of the layer of the inorganic layered compound is peeled and dispersed in water into an emulsion in which resin primary particles are stably dispersed, By aggregating and drying the mixed solution in which the layered compound and the fluororesin primary particles are uniformly dispersed, a dry powder of the aggregate in which the resin primary particles and the inorganic layered compound are uniformly dispersed is obtained. The primary particles of the resin used will serve as mere physical particles. Therefore, any resin emulsion obtained by emulsion polymerization can be used regardless of the chemical properties, molecular structure, melting point, crystallization temperature, melt viscosity, etc. of the resin used. However, the melt viscosity or melt flow rate (MFR) range of the resin emulsion to be used can be determined in accordance with the purpose in order to melt-mold the aggregated dry powder. For example, the melt viscosity of the perfluorofluororesin composite composition is such that the melt flow rate (MFR) at 372 ° C. is 0.5 to 100 g / 10 min for melt molding such as melt extrusion molding and injection molding, preferably Is in the range of 0.5-50 g / 10 min.

  Specific examples of the inorganic layered compound having a swelling or cleavage property used in the present invention include, for example, natural or synthetic bentites, saponites, stevensites, beidellites, montmorillonites, bentonites, and other smectite group clay minerals and Na-type tetrasilicates. Examples thereof include swellable mica group clay minerals such as thick fluorine mica, Li-type tetrasilicic fluorine mica, Na salt-type fluorine teniolite, Li-type fluorine teniolite, and vermiculite, or substitutions and derivatives thereof, or a mixture thereof.

  In addition, the substituted body includes those in which a part of Na ions or Li ions in the interlayer ions are substituted with K ions, and a part of Si ions in the tetrahedral sheet are substituted with Mg ions. It is. Commercially available products include Laponite XLG (synthetic hectorite similar substance manufactured by LaPorte, UK), Laponite RD (Hextrite similar substance manufactured by LaPorte, UK), Smecton SA-1 (Naponite similar substance manufactured by Kunimine Industries), Bengel (Hoyoyo Yoko Natural montmorillonite sold), Kunipia F (natural montmorillonite sold by Kunimine Industries), Veegum (natural hectorite manufactured by Vanda-Bilt, USA), Daimonite (synthetic swellable mica manufactured by Topy Industries), Cloisite (Southern USA, USA) Montmorillonite manufactured by Clay), Somasif (MF-100, synthetic swelling mica manufactured by Coop Chemical), SWN (synthetic smectite manufactured by Coop Chemical), and the like.

  Among the swellable inorganic layered compounds, swellable mica obtained by heat-treating a mixture of talc and alkali silicofluoride is preferable, and a fine powder obtained by mixing talc and sodium silicofluoride and / or lithium silicofluoride is 600 ° C to What is obtained by heat-processing at 1200 degreeC is still more preferable.

  The particle size of the inorganic layered compound raw material of the present invention depends on the purpose of use, but for the purpose of high zero shear viscosity, the particle size is 10,000 nm or less, preferably 5,000 nm or less. The aspect ratio (particle size / thickness) of the inorganic layered compound in a state of being uniformly dispersed in the fluororesin matrix at the nano level is 40 or more, preferably 100 or more.

  In the present invention, the fluororesin primary particles are surrounded by a surfactant and stably dispersed in a solvent, and a dispersion containing an inorganic layered compound having a property of swelling or cleaving into a dispersion medium; In order to prepare an aqueous dispersion in which the resin primary particles and the swelled or cleaved inorganic layered compound are uniformly mixed, the powder of the inorganic layered compound is directly put into the perfluorofluororesin emulsion and stirred and mixed. However, in order to uniformly mix the fluororesin primary particles and the inorganic layered compound powder, if a strong shearing force is applied to the mixed solution, the surfactant of the fluororesin primary particles is destroyed and the perfluoro fluororesin emulsion is not effective. It may become stable and a uniform mixed solution may not be obtained. Therefore, from the viewpoint that the inorganic layered compound can be finely and uniformly dispersed in the mixed liquid, the inorganic layered compound powder is previously placed in water, and the inorganic layered compound concentration is 0.5% of the amount of water. The range of 20% by weight to 30% by weight and the temperature is preferably in the range of 20 ° C. to 80 ° C. Also, depending on the type and structure of the stirrer used, 2 under stirring (mechanical stirring and / or ultrasonic treatment) It is preferable to mix the inorganic layered compound by mixing for at least hours, preferably at least 4 hours, more preferably at least 6 hours. In the aqueous dispersion containing the inorganic layered compound thus obtained, water enters and swells between the layers of the inorganic layered compound, and a part of the inorganic layered compound is peeled off and dispersed in water. (Clay and Cray Minerals, vol. 32, P320, 1984). In addition, when stirring the aqueous dispersion containing the inorganic layered compound, by vigorously stirring, some of the inorganic layered compound layers are shifted from each other, so that the so-called inorganic layered compound layer is cleaved or further cleaved. As a result, the inorganic layered compound layer can be peeled off.

  Accordingly, a perfluoro fluororesin emulsion in which primary particles of the fluororesin are stably dispersed in a dispersion containing the inorganic stratiform compound in which a part of the inorganic stratiform compound layer is previously cleaved or peeled and dispersed in water. By further mixing and mixing, the peeling of the cleaved layer further proceeds, and it is possible to obtain a mixed liquid in which the inorganic layered compound and the inorganic layered compound and the fluororesin primary particles are uniformly dispersed.

  As a method of aggregating the aqueous dispersion in which the resin primary particles and the inorganic layered compound are uniformly mixed, the aqueous dispersion is frozen at a temperature of 0 ° C. or lower, or an ionic strength or pH of the mixture is adjusted by adding an electrolytic substance. The method of changing or applying a shear force can be mentioned.

  More specifically, the method of applying a shearing force to an aqueous dispersion contains a resin emulsion and an inorganic layered compound in which a part of the inorganic layered compound layer is peeled off and dispersed in water with a strong shearing force by a stirring device. This is a method (physical agglomeration) in which the mixed liquid composed of the dispersion is stirred to break down the micelle structure of the surfactant in the fluororesin emulsion.

  The method of changing the ionic strength or pH of a mixed solution by adding an electrolytic substance to an aqueous dispersion is more specifically changing the ionic strength or pH by adding an electrolytic substance to a mixed solution of a resin emulsion and an inorganic layered compound. This is a method (chemical agglomeration) in which the stability of the mixed solution of the resin emulsion and the inorganic layered compound is abruptly reduced and agglomerated.

  More specifically, the method of freezing an aqueous dispersion mixture at a temperature of 0 ° C. or less is more specifically by pressing colloidal particles between ice crystals by the growth of ice crystals generated by freezing the resin emulsion and the inorganic layered compound mixture. It is a method of aggregation (freeze aggregation).

In particular, the stability of the resin emulsion or the mixed solution is suddenly lowered by adding an electrolytic substance or an inorganic salt to the mixed solution of the perfluoro fluorine resin emulsion and the dispersion containing the inorganic layered compound, so that the resin primary particles are suddenly reduced. A chemical agglomeration method is preferred in which a homogeneous mixture state of the inorganic layered compound is fixed to obtain an agglomerate in which different kinds of particles are uniformly dispersed. Depending on the type and proportion of the primary resin particles or inorganic layered compound in the mixture before chemically agglomerating, it is used, for example, for the purpose of chemically aggregating primary fluororesin particles in a perfluorofluororesin emulsion. Examples of the electrolytic substance include inorganic or organic substances such as HCl soluble in water, H ₂ SO ₄ , HNO ₃ , H ₃ PO ₄ , Na ₂ SO ₄ , MgCl ₂ , CaCl ₂ , sodium formate, potassium acetate, and ammonium carbonate. The compound of can be illustrated. Among these, volatilizable compound in the drying process of the agglomerate after, for example HCl, HNO _3, preferably used and ammonium carbonate. In addition to the above electrolytic substances, halogen hydroacid, phosphoric acid, sulfuric acid, molybdic acid, alkali metal salt of nitric acid, alkaline earth metal salt, ammonium salt, etc., preferably potassium bromide, potassium nitrate, potassium iodide (KI), Inorganic salts such as ammonium molybdate, sodium dihydrogen phosphate, ammonium bromide (NH ₄ Br), potassium chloride, calcium chloride, copper chloride, and calcium nitrate can be used alone or in combination. The amount of these electrolytic substances used depends on the type of electrolytic substance and the solid content concentration of the dispersion containing the fluororesin emulsion and the inorganic layered compound, but the perfluorofluororesin emulsion and the dispersion containing the inorganic layered compound It is preferably used in a proportion of 0.001 to 5% by weight, particularly 0.05 to 1% by weight, based on the weight of the mixed solution. Moreover, it is preferable to add in the form of aqueous solution to the liquid mixture of a perfluoro fluororesin emulsion and an inorganic layered compound. When the amount of the electrolytic substance used is too small, there is a place where agglomeration occurs partly slowly, so that it is impossible to fix the uniform mixed state of the resin primary particles and the inorganic layered compound at a stretch as a whole. In some cases, it is not possible to obtain a perfluorofluororesin composite composition in which the compound is uniformly dispersed in the resin.

  In addition, depending on the solid content concentration of the dispersion containing the perfluorofluororesin emulsion and the inorganic layered compound, the dispersion containing the perfluorofluororesin emulsion and the inorganic layered compound is stirred to obtain a uniform mixed solution. It is also possible to dilute the dispersion containing the perfluorofluororesin emulsion or the inorganic layered compound in advance with pure water or the like to adjust the solid content concentration, and then stir and mix.

  An apparatus that stirs the perfluoro fluororesin emulsion and the dispersion containing the inorganic layered compound to uniformly mix the resin primary particles and the inorganic layered compound, and then further physically or chemically aggregates the mixture. Although not particularly limited, it is preferable that the apparatus is equipped with a stirring means capable of controlling the stirring speed, for example, a propeller blade, a turbine blade, a paddle blade, a paddle blade, a horseshoe blade, a spiral blade, and a drainage device. . In such a device, an electrolytic substance or an inorganic salt is placed in a mixed liquid of a perfluoro fluororesin emulsion and an inorganic layered compound or a dispersion containing the inorganic layered compound, and stirred to obtain a resin colloidal particle or / and an inorganic layered compound. Agglomerate to form aggregates of different particles, which are separated from the aqueous medium. The stirring speed in the step of separating the aqueous medium from the aggregate is preferably 1.5 times faster than the stirring speed in the mixing step of the dispersion containing the perfluorofluororesin emulsion and the inorganic layered compound. The aggregate of the different types of particles is discharged from the aqueous medium, washed with water as necessary, and then dried at a temperature equal to or lower than the melting point of the resin or the thermal decomposition start temperature to obtain a powder of the perfluorofluororesin composite composition. The drying temperature is preferably in a temperature range in which the electrolytic substance, the surfactant, and the like can be volatilized within a temperature at which thermal degradation or decomposition of the perfluorofluororesin does not occur. Further, when the inorganic layered compound is sufficiently swollen or cleaved in the dispersion medium, a resinous colloidal particle or / and a gel-like aggregate obtained by agglomerating the inorganic layered compound are obtained by adding an electrolytic substance or an inorganic salt and stirring. May not be separated from water by stirring, but in this case, the gel-like aggregate may be dried as it is.

  The ratio of the inorganic layered compound to the perfluorofluororesin composite composition is 0.1 to 30% by weight, more preferably 0.3 to 20% by weight, although it depends on the use of the perfluororesin composite composition. Preferably it is 0.5 to 15% by weight. A nano-resin composite mixture in which inorganic layered compounds are dispersed at a nano level in a resin or a so-called polymer nano-composite has a smaller space between the nanoparticles and the resin matrix than a conventional resin composite mixture in which a filler is dispersed at a micron level. Therefore, there is an advantage that the physical properties can be improved even if the inorganic layered compound is added in a smaller amount than the conventional resin composite mixture.

A general polymer concentrated solution or melt is a typical non-Newtonian fluid, and changes depending on the viscosity shear rate. When the shear rate increases, the viscosity decreases, and when the shear rate decreases, the viscosity decreases. To increase. However, as the shear rate is further reduced, it gradually approaches a constant value. This limit value is called zero shear viscosity (η *, Zero Shear Rate Viscosity), and is one of the most important physical quantities representing the viscosity of a polymer, and is represented by an exponential function of molecular weight.
For example, the melt viscosity of a perfluoro fluororesin usually approaches a constant value as the shear rate decreases, and exhibits a Newtonian fluid behavior (A in FIG. 1). In addition, the conventional resin composite mixture in which the inorganic layered compound is dispersed in the perfluorofluororesin also has a viscosity that is higher at a substantially constant rate than the perfluorofluororesin that does not contain the inorganic layered compound. When the velocity decreases, the value approaches a constant value, and the behavior is almost Newtonian fluid (B in FIG. 1).

  However, the perfluorofluororesin composite composition of the present invention in which the inorganic layered compound is uniformly nano-dispersed in the perfluorofluororesin, the melt viscosity does not approach a constant value even if the shear rate decreases, When the shear rate is decreased, the viscosity is further increased, and non-Newtonian fluid behavior is exhibited (C and D in FIG. 1). In this way, the perfluoro fluororesin composite composition in which the inorganic layered compound is uniformly dispersed in the perfluoro fluororesin matrix at the nano level has a higher viscosity when the shear rate is reduced. It can be used for applications where high temperature droplets are difficult to fall off (drip prevention) when a fire breaks out.

In the case of the perfluorofluororesin composite composition of the present invention, the viscosity at ₁ rad / sec (V ₁ ) and the viscosity at 0.1 rad / sec measured at 340 ° C. in the parallel plate mode of the dynamic viscoelasticity measuring apparatus. the ratio of _{(V 0.1) (V 0.1 /} V 1) , depending on the particle diameter of the mixing ratio and the inorganic fine particles of the perfluoropolymer primary particles and the inorganic laminar compound, 1.5 or more, preferably Is 2.0 or more, more preferably 3.0 or more.

  In the present invention, the dried powder of the aggregate of different particles in which the primary particles of the fluorofluororesin and the inorganic layered compound obtained in the aggregation / drying step are uniformly dispersed is formed into pellets through an ordinary melt extruder and then extruded. Melt molding such as molding, injection molding, transfer molding and blow molding can be performed. Of course, the agglomerated powder of different kinds of particles not pelletized as described above is directly used as a molding raw material, or the agglomerated powder dried by a compactor is hardened by a molding machine hopper to improve the bite of the agglomerated powder. It can also be melt-molded. Depending on the purpose of use, the agglomerated powder of different kinds of non-pelletized particles tends to have a higher elastic modulus and lower shear rate viscosity (zero shear viscosity) and lower elongation than those pelletized. Aggregate powders or pellets can be selected (see Tables 1 and 2). Further, in the process of pelletizing through a melt extruder, additives can be optionally blended or blended with other resins within a range where the physical properties of the perfluorofluororesin are not impaired. Additives can be blended not only in the melt extrusion process, but also in the mixing process of the resin emulsion and the aqueous dispersion of the inorganic layered compound. Examples of such additives include glass fiber, carbon fiber, aramid fiber, graphite, carbon black, fullerene, carbon nanotube, carbon nanofiber, silicon oxide, titanium oxide, and silver nanoparticles. Furthermore, the powder of the aggregate of the different particle | grains in which the perfluoro fluororesin primary particle | grains obtained by this invention and an inorganic layered compound are disperse | distributed further is further granulated, and it uses also as a material for powder molding, powder coating, and rotation molding be able to.

  The melt molding method and conditions for obtaining the molded product of the present invention are not particularly limited, and tubes, sheets, films, rods, fibers, and electric wire coatings that have been conventionally applied to hot-melt fluoropolymers. The extrusion conditions for the above, the blow molding conditions for containers and the like, and the injection molding conditions for trays and the like can be used as they are. Powder molded products, powder coating molded products, and rotational molded products can also be obtained.

  The type of the final product to be produced is not particularly limited, and can be applied to any field where improvement of the effect can be expected by uniformly dispersing the particles in the resin at the nano level. For example, there are tubes, sheets, films, rods, fibers, fibers, packings, linings, seal rings, electric wire coating, printed circuit boards, and the like. In particular, if the particles are uniformly dispersed in the resin at the nano level, the zero shear viscosity when the shear rate is very low is much higher than when the particles are not nano-dispersed. It can also be used for applications where high temperature droplets are difficult to fall off when drip occurs (anti-drip).

The present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples.
In the present invention, each physical property was measured by the following method.

A. Measurement of physical properties (1) Melting point (melting peak temperature)
A differential scanning calorimeter (Pyris 1 type DSC, manufactured by Perkin Elmer) was used. About 10 mg of a sample is weighed and placed in a dedicated aluminum pan, crimped by a dedicated crimper, stored in the DSC body, and heated from 150 ° C. to 360 ° C. at a rate of 10 ° C./min. The melting peak temperature (Tm) was determined from the melting curve obtained at this time.

(2) Melt flow rate (MFR)
Using a melt indexer (manufactured by Toyo Seiki Co., Ltd.) equipped with a corrosion-resistant cylinder, die and piston according to ASTM D1238-95, 5 g of sample powder is filled into a cylinder maintained at 372 ± 1 ° C. and held for 5 minutes. After that, it was extruded through a die orifice under a load of 5 kg (piston and weight), and the extrusion speed (g / 10 minutes) at this time was determined as MFR.

(3) Dispersion state of inorganic layered compound Three specimens of 10 mm × 10 mm were cut out from a sample having a thickness of about 200 μm prepared by melt compression molding a perfluorofluororesin composite composition sample at 350 ° C., and optical ( Using a polarizing microscope (made by NIKON, OPTIPHOT2-POL), the dispersion state was evaluated for the presence of aggregates composed of inorganic layered compounds having a size of 10 μm or more. Only a sample in which an aggregate composed of an inorganic layered compound of 10 μm or more is not observed, a 15 mm × 8 mm specimen is cut out, solidified with an epoxy resin, embedded into a thin film having a thickness of 70 nm with an ultramicrotome, and a transmission electron microscope (Phillips CM-300) was used to observe the dispersion state (particle diameter and thickness) of the inorganic layered compound in the perfluorofluororesin, and evaluated according to the following criteria.
A: Most inorganic layered compounds are nano-dispersed to a thickness of 50 nm or less.
◯: A few aggregates of inorganic layered compound remain.
X: Many aggregates of inorganic layered compounds of 10 μm or more remain with an optical microscope.

(4) Tensile properties (tensile strength, elongation, tensile modulus)
A perfluoro fluororesin composite composition was measured from a sample having a thickness of about 1 mm prepared by melt compression molding at 350 ° C. according to JIS K 7127 at a pulling rate of 50 mm / min.

(5) Melt viscosity ratio (zero shear viscosity ratio)
A test specimen having a diameter of 25 mm is made from a sheet-like sample having a thickness of about 1.5 mm prepared by melt-compression molding a perfluorofluororesin composite composition sample at 350 ° C., and an ARES viscoelasticity measuring device manufactured by Rheometric Scientific The melt viscosity was measured in a frequency (shear rate) range of 100 to 0.1 rad / sec at 340 ° C. The ratio (V _0.1 / V ₁ ) of the viscosity (V ₁ ) at ₁ rad / sec and the viscosity (V _0.1 ) at _0.1 rad / sec was calculated.

(6) Analysis of X-ray diffraction results A 20 mm × 20 mm specimen was cut from a sheet-like sample having a thickness of about 1.5 mm produced by melt compression molding a perfluorofluororesin composite composition sample at 350 ° C. Using X-ray wide-angle scattering measurement equipment (RIGAKU, Cu Kα radiation, wavelength: 0.154 nm), X-ray analysis is performed by the reflection method, and inorganics in perfluoro fluororesin such as the spacing and thickness of inorganic layered compounds The dispersion structure of the layered compound was evaluated (Element of X-Ray Diffraction, Addison-Wesley, Reading, MA, 1978, P99-P106).
In addition, in order to investigate the inorganic layered compound dispersion structure in the aqueous dispersion composed of the inorganic layered compound dispersed in water before mixing with the PFA emulsion, the aqueous dispersion of the inorganic layered compound is thinly coated on the glass, The X-ray diffraction measurement was performed as it was, and the interplanar spacing and thickness of the inorganic layered compound in the aqueous dispersion were determined.

B. Raw materials The raw materials used in Examples and Comparative Examples of the present invention are as follows.
(1) Perfluoro fluororesin emulsion PFA aqueous dispersion obtained by emulsion polymerization (Mitsui / DuPont Fluorochemicals) (PFA solid content: 29% by weight, average particle diameter of PFA primary particles: 200 nm, pH: 9, melting point: 309 ° C., melt flow rate: 2 g / 10 min).

(2) Inorganic layered compound (a) ME-100 (manufactured by Coop Chemical Co., Ltd., swellable synthetic mica, particle size: 2 to 5 μm)
(B) SWN (manufactured by Coop Chemical Co., Ltd., swellable synthetic smectite, particle size: about 0.05 μm)
(C) Kunipia F (Kunimine Industries, Na-montmorillonite, particle size: about 2 μm)

(Example 1)
10.53 g of swellable synthetic mica (ME-100) and 500 g of pure water were placed in a beaker (2 L), stirred for 6 hours at 350 rpm using a downflow type propeller type four-blade stirring device, and then for another 15 minutes. To the dispersion of ME-100 obtained by sonication, 687.3 g of an aqueous PFA dispersion was added so that the ME-100 content was 5% by weight with respect to the PFA resin composite, and 30 minutes at 350 rpm. After stirring, 6 g of 60% nitric acid was added, and PFA primary particles and ME-100 particles were agglomerated at a stretch while stirring until gelation progressed and stirring was not possible. The obtained gel-like aggregate was further stirred at 450 rpm for 5 minutes to remove excess water from the aggregate, and the remaining aggregate was dried at 170 ° C. for 10 hours to obtain a dry powder of the aggregate. Aggregate dry powder (hereinafter referred to as pre-melt mixed sample) is compression molded at 350 ° C., and using the obtained samples having a thickness of about 1.0 mm and 1.5 mm, tensile physical properties / MFR measurement, optical / transmission electron Microscopic observation and viscosity measurement were performed, and the results are shown in Tables 1 and 2. Further, the dry powder of the agglomerate was further melt-mixed at 350 ° C. and 100 rpm for 3 minutes using a melt mixing apparatus (R-60 batch mixer manufactured by Toyo Seiki Seisakusho) to obtain a perfluorofluororesin composite composition (hereinafter referred to as “the perfluoro fluororesin composite composition”). Sample after melt mixing). After melt-mixing into small pieces having a size of about 3 mm, the sample was compression molded at 350 ° C., and physical properties were measured using the obtained sample having a thickness of about 1.0 mm. Tables 3 and 4 show the results. Furthermore, Table 5 shows the X-ray measurement results. From the result of X-ray analysis, the thickness (H ₀₀₁ ) of the layered compound dispersed in the fluororesin matrix was 11.3 nm. Further, from observation with a transmission electron microscope, it was confirmed that ME-100 having a thickness of about 10 nm was dispersed in the fluororesin matrix (FIG. 2). For reference, the thickness of ME-100 in the aqueous dispersion was 15.8 nm.

(Example 2)
Place 15.05 g of swellable synthetic mica (ME-100) and 500 g of pure water in a beaker, stir at 350 rpm for 6 hours using a downflow type propeller type four-blade stirrer, and then sonicate for another 15 minutes. 687.3 g of an aqueous PFA dispersion was added to the ME-100 dispersion obtained in such a manner that the ME-100 content was 7% by weight with respect to the PFA resin composite, and the aggregates were obtained in the same procedure as in Example 1. A dry powder and a melt-mixed fluororesin composite composition were obtained. The dry powder and the melt-mixed perfluorofluororesin composite composition are compression molded at 350 ° C., and the physical property measurement results of the obtained samples are shown in Table 1, Table 2, Table 3, and Table 4. Furthermore, Table 5 shows the X-ray measurement results. From the X-ray analysis result, the thickness (H ₀₀₁ ) of the layered compound dispersed in the fluororesin matrix was 10.6 nm.

(Example 3)
Put 22.2 g of swellable synthetic mica (ME-100) and 500 g of pure water into a beaker and stir for 6 hours at 350 rpm using a down flow type propeller type four-blade stirrer and then sonicate for another 15 minutes 687.3 g of an aqueous PFA dispersion was added to the dispersion of ME-100 obtained in such a manner that the ME-100 content was 10% by weight with respect to the PFA resin composite, and the same procedure as in Example 1 was performed. A dry powder of the aggregate and a melt-mixed fluororesin composite composition were obtained. The dry powder and the melt-mixed perfluorofluororesin composite composition are compression molded at 350 ° C., and the physical property measurement results of the obtained samples are shown in Table 1, Table 2, Table 3, and Table 4. Furthermore, Table 5 shows the X-ray measurement results. From the result of X-ray analysis, the thickness (H ₀₀₁ ) of the layered compound dispersed in the fluororesin matrix was 10.2 nm.

Example 4
10.53g of swellable synthetic mica (ME-100) and 500g of pure water are put into a beaker and stirred for 2 hours at 350rpm using a down flow type propeller type 4 blade impeller and then sonicated for another 15 minutes. 687.3 g of an aqueous PFA dispersion was added to the ME-100 dispersion obtained in such a manner that the ME-100 content was 5% by weight with respect to the PFA resin composite, and the aggregates were obtained in the same procedure as in Example 1. A dry powder and a melt-mixed fluororesin composite composition were obtained. The dry powder and the melt-mixed perfluorofluororesin composite composition are compression molded at 350 ° C., and the physical property measurement results of the obtained samples are shown in Table 1, Table 2, Table 3, and Table 4. Furthermore, Table 5 shows the X-ray measurement results. From the result of X-ray analysis, the thickness (H ₀₀₁ ) of the layered compound dispersed in the fluororesin matrix was 25 nm. Further, from observation with a transmission electron microscope, it was confirmed that ME-100 having a thickness of about 20 nm was dispersed in the fluororesin matrix.

(Example 5)
It was obtained by putting 10.53 g of synthetic smectite (SWN) and 500 g of pure water into a beaker, stirring for 6 hours at 350 rpm using a downflow type propeller type stirring with four blades, and then sonicating for another 15 minutes. The dispersion of SWN was charged with 687.3 g of an aqueous PFA dispersion so that the SWN content was 5% by weight with respect to the PFA resin composite. A resin composite composition was obtained. The dry powder and the melt-mixed perfluorofluororesin composite composition are compression molded at 350 ° C., and the physical property measurement results of the obtained samples are shown in Table 1, Table 2, Table 3, and Table 4. Furthermore, Table 5 shows the X-ray measurement results. Since the SWN diffraction peak disappeared in the X-ray diffraction pattern of the sample in which SWN was dispersed in the PFA matrix, it was found that SWN was completely peeled and nano-dispersed in the PFA matrix (FIG. 3). Therefore, from the X-ray analysis result, the thickness (H ₀₀₁ ) of SWN dispersed in the fluororesin matrix is 1 nm in calculation. Moreover, it was confirmed from transmission electron microscope observation that SWN having a thickness of about 1 nm was dispersed in the fluororesin matrix (FIG. 4). For reference, the thickness of SWN in the aqueous dispersion was 2.5 nm.

(Example 6)
10.53 g of Na-montmorillonite (Kunipia F) and 500 g of pure water are put in a beaker and stirred for 6 hours at 350 rpm using a downflow type propeller type four-blade stirrer and then sonicated for another 15 minutes. 687.3 g of an aqueous PFA dispersion was added to the obtained dispersion of Kunipia F so that the content of Kunipia F was 5% by weight with respect to the PFA resin composite. A melt-mixed perfluorofluororesin composite composition was obtained. The dry powder and the melt-mixed fluororesin composite composition are compression molded at 350 ° C., and the physical property measurement results of the obtained samples are shown in Table 1, Table 2, Table 3, and Table 4. Furthermore, Table 5 shows the X-ray measurement results. Since the diffraction peak of Kunipia F disappeared in the X-ray diffraction pattern of the sample in which Kunipia F was dispersed in the PFA matrix, it can be seen that Kunipia F was completely exfoliated and nano-dispersed in the PFA matrix (FIG. 5). ). Therefore, the thickness (H ₀₀₁ ) of the Kunipia F dispersed in the fluororesin matrix is 1 nm in calculation from the X-ray analysis result. For reference, the thickness of Kunipia F in the aqueous dispersion was 6 nm.

(Comparative Example 1)
350 g of swellable synthetic mica (ME-100) and 63 g of PFA powder obtained by agglomerating and drying the aqueous PFA dispersion of Example 1 were used, using a melt mixing apparatus (R-60 batch mixer manufactured by Toyo Seiki Seisakusho). The mixture was melted and mixed at 100 ° C. for 3 minutes to obtain a perfluorofluororesin composite composition. Tables 2 and 4 show the physical property measurement results of the samples obtained by compression molding the fluororesin composite composition at 350 ° C. For the results before melt mixing in Tables 1 and 3, the results of the melt-mixed samples were substituted. Further, from the observation result with a polarizing microscope, a large number of non-nano-dispersed ME-100s having a size of about 150 μm were observed, and thus X-ray and transmission electron microscope observations were not performed.

(Reference example)
Tables 2 and 4 show physical properties of only the fluororesin in which the use of the inorganic layered compound is omitted. For the results before melt mixing in Tables 1 and 3, the results of the melt-mixed samples were substituted.

  From the X-ray diffraction and transmission electron microscope observation results, it can be seen that in any of Examples 1 to 6 of the present invention, the inorganic layered compound having a thickness of 25 nm or less is uniformly dispersed at the nano level in the PFA matrix. I understood. However, in Comparative Example 1 in which the inorganic layered compound and PFA were directly melt-mixed, a large number of inorganic layered compounds having a size of 100 μm or more were observed even with an optical microscope.

  For the samples before melt mixing shown in Table 1, the fluororesin composite compositions (Examples 1 to 6) according to the present invention have higher tensile elastic modulus than that of PFA alone, and have an inorganic layered compound content. It became higher with the increase. However, the elongation was very low. In addition, the MFR of the sample in Examples 1 to 6 of the present invention is expressed as 0.2 g / 10 min or less because the melt strand slightly came out of the die during measurement and the sample for measurement could not be collected. did.

Also, the viscosity ratio of the sample before melt-mixing in Table 3, the viscosity ratio of a sample inorganic layered compound is nano-dispersed in the PFA matrix (Examples 1 to _{6) (V 0.1 / V 1} ) Was 4 or higher, indicating a very high zero shear viscosity (except for Example 4). However, the non-nanodispersed sample (Comparative Example 1) and the PFA simple substance (Reference Example 1) have a viscosity ratio (V _0.1 / V ₁ ) of 1.3 or less and hardly exhibit thixotropic properties.

About the sample after the melt mixing of Table 2, the elongation rate of the inorganic layered compound 5% sample (Example 1, Example 4, Example 5, Example 6) increased to about 200% or more by the melt mixing. Further, the viscosity ratio (V _0.1 / V ₁ ) of the samples (Example 1 to Example 6) in which the inorganic layered compound is nano-dispersed in the PFA matrix by melt mixing is 55% to 85% of the sample before melt mixing. %, But showed a sufficiently high zero shear viscosity compared to PFA alone. In particular, in the case of Example 5 containing 5% by weight of SWN, the viscosity ratio (V _0.1 / V ₁ ) was 4.5 even after melt mixing, indicating a very high zero shear viscosity. This is presumably because delaminated SWN having a size of about 50 nm and a thickness of about several nm was uniformly dispersed in the PFA matrix at the nano level.

  In the present invention, a fluororesin primary particle is surrounded by a surfactant (hereinafter sometimes referred to as an emulsifier) and is stably dispersed in a solvent. Alternatively, the dispersion containing the inorganic layered compound having the cleaving property is stirred, and the aqueous dispersion in which the resin primary particles and the swollen or cleaved inorganic layered compound are uniformly mixed is frozen at a temperature of 0 ° C. or lower. Or after adding an electrolytic substance to change the ionic strength or pH of the mixed solution or applying a shearing force to fix the uniform mixed state of the fluororesin primary particles and the inorganic layered compound (hereinafter this process is agglomerated) The resulting agglomerates are separated from the aqueous solution and dried to uniformly disperse the inorganic layered compound in the fluororesin at the nano level. Excellent sex, provides a zero shear viscosity is high perfluoropolymer composite composition.

The types of molded products produced from the perfluorofluororesin composite composition of the present invention can be applied to all fields where improvement of the effect can be expected by uniformly dispersing the inorganic layered compound in the fluororesin at the nano level. can do. For example, tubes, sheets, films, rods, fibers, fibers, packings, linings, seals can be obtained by compression molding, extrusion molding, transfer molding, blow molding, injection molding, lining, etc. It can be used for rings and wire coating.
The perfluorofluororesin composite composition provided by the present invention is not nanodispersed in zero shear viscosity when the shear rate is very low when the inorganic layered compound is uniformly dispersed in the fluororesin at the nano level. Because it is very high compared to the case, it is ideal for applications where high-temperature liquid droplets are difficult to drop (anti-drip) when a fire occurs in a resin product such as an electric wire.

It is a shear viscosity measurement result of a perfluoro fluorine resin composite composition. 2 is a transmission electron micrograph of the perfluorofluororesin composite composition used in Example 1. FIG. 6 is an X-ray diffraction pattern of an aqueous dispersion of a perfluorofluororesin composite composition and SWN alone used in Example 5. FIG. 6 is a transmission electron micrograph of the perfluorofluororesin composite composition used in Example 5. FIG. 7 is an X-ray diffraction pattern of an aqueous dispersion of a perfluorofluororesin composite composition and Kunipia F used alone in Example 6. FIG.

Claims (11)

A resin composite composition in which an inorganic layered compound having a property of swelling or cleaving in a dispersion medium is dispersed in a perfluoro fluororesin, and measured at 340 ° C. in a parallel plate mode of a dynamic viscoelasticity measuring apparatus. The ratio of the viscosity (V ₁ ) at ₁ rad / sec to the viscosity (V _0.1 ) at _0.1 rad / sec (V _0.1 / V ₁ ) is 1.5 or more. object.   2. The perfluoro fluorine according to claim 1, wherein the perfluoro fluorine resin is a polymer or copolymer of a monomer selected from tetrafluoroethylene, hexafluoropropylene, and perfluoro (alkyl vinyl ether). Resin composite composition.   The inorganic layered compound having a property of swelling or cleaving into the dispersion medium is an inorganic layered compound selected from the group consisting of smectite group viscosity minerals, swellable mica group viscosity minerals, and combinations thereof. Item 3. The perfluorofluororesin composite composition according to Item 1 or 2.   The content of the inorganic layered compound in the perfluorofluororesin composite composition is 0.5 to 15% by weight with respect to the fluororesin composite. Fluoro-fluorine resin composite composition.   The perfluorofluororesin composite composition according to any one of claims 1 to 4, wherein the inorganic layered compound dispersed in the perfluorofluororesin composite composition has a thickness of 100 nm or less.   Separation of aqueous components from aggregates obtained by agglomerating an aqueous dispersion mixture obtained by mixing an emulsion of perfluoro fluororesin and a dispersion containing an inorganic layered compound that swells or cleaves into a dispersion medium while stirring. -The manufacturing method of the perfluoro fluororesin composite composition in any one of Claims 1-5 obtained by drying.   The aggregate is obtained by agglomerating the aqueous dispersion mixture by freezing at a temperature of 0 ° C. or lower, adding an electrolytic substance to change the ionic strength or pH of the mixture, or applying a shearing force. The method for producing a perfluorofluororesin composite composition according to claim 6, wherein   The pellet obtained by melt-extruding the perfluoro fluorine resin composite composition according to any one of claims 1 to 5.   The electric wire or electric wire covering jacket which consists of a perfluoro fluororesin composite composition in any one of Claims 1-5.   The pipe | tube or sheet | seat which consists of a perfluoro fluororesin composite composition in any one of Claims 1-5.   A blow molded article comprising the perfluorofluororesin composite composition according to claim 1.

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